WO2004007584A1

WO2004007584A1 - Blowing agent having low vapor pressure, premix, and process for producing foam

Info

Publication number: WO2004007584A1
Application number: PCT/JP2003/009042
Authority: WO
Inventors: Takashi Shibanuma; Tatsumi Tsuchiya; Yasufu Yamada; Noriaki Shibata
Original assignee: Daikin Industries, Ltd.
Priority date: 2002-07-16
Filing date: 2003-07-16
Publication date: 2004-01-22
Also published as: JP3952185B2; AU2003280979A1; JP2004099862A

Abstract

A process for producing a synthetic resin foam which comprises reacting at least one polyol with at least one polyisocyanate compound in the presence of a blowing agent, characterized in that the blowing agent is a mixture comprising a combination of at least one glycol compound and/or at least one amide compound with 1,1,1,3,3-pentafluoropropane.

Description

Specification

TECHNICAL FIELD The present invention relates to a foaming agent having a low vapor pressure, a premix, and a method for producing a foam.

The present invention relates to a method for producing a synthetic resin foam, a foaming agent for producing a synthetic resin foam, and a premix.

Background art

It is widely practiced to react a polyol and a polyisocyanate conjugate in the presence of a catalyst and a foaming agent to produce a synthetic resin foam. Examples of the obtained synthetic resin foam include polyurethane and polyisocyanurate.

As a foaming agent used in the production of synthetic resin foams such as the above-mentioned polyurethane foams, trichlorofluoromethane (CFC-11) has been mainly used so far.

In recent years, it has been pointed out that certain chlorofluorocarbons, when released into the atmosphere, destroy the stratospheric ozone layer and, as a result, have serious adverse effects on human ecosystems, including humans. For this reason, the use of chlorofluorocarbon, which has a high risk of depletion of the ozone layer, is restricted by international agreements. CFC-11 above is subject to this usage restriction. From this point, the ozone layer should not be destroyed, or its risk is low! / It is necessary to develop a new blowing agent.

At present, 1.1-fluorochrome-one-fluoroene (HCFC-141b) is used as a substitute for CFC-11 as a fluorocarbon with a small effect on the ozone layer.

However, since this substance also contains chlorine atoms in the molecule, there is still a danger of destroying the ozone layer.

JP-A-2-29440, JP-A-2-235982, etc. disclose a method for producing a foam using a fluorinated hydrocarbon that does not contain chlorine and has no risk of destroying an ozone layer. I have. Japanese Patent Application Laid-Open No. 5-239251 discloses that 1,1,1,3,3-pentafluoropropane (HFC-245fa) is used as a foaming agent for producing a plastic foam. You.

HFC-245fa is a nonflammable compound with a boiling point of 15 ° C and is a fluorinated hydrocarbon containing hydrogen atoms, so it is considered that there is no danger of ozone layer destruction. Furthermore, HFC-245fa has attracted attention as a very promising candidate for a foaming agent to replace HCFC-141b because its boiling point is close to that of CFC-11 and HCFC-141b, and its force is nonflammable. Although the boiling point of HFC-245fa (15 ° C) is acceptable, CFC-11 (boiling point 24 ° C) and

Slightly lower than HCFC-141b (boiling point 32 ° C). Therefore, when the environmental temperature is high, the production of the foam becomes difficult due to rapid evaporation. Further, the solubility in the polyol is not always high, and a premix containing HFC-245fa and the polyol may cause phase separation. For this reason, there is a problem that the usable polyol is limited.

In the case of a foaming agent with a low boiling point and low solubility in polyols, poor mixing, residual unreacted components, and coarse bubbles called poids occur when the polyol is mixed with the isocyanate compound to produce a foam. As a result, the strength and thermal conductivity required for the rigid urethane foam are deteriorated. In addition, HFC-245fa itself or a mixture with a foam material (particularly a premix that is a mixture with a polyol) has a considerably high vapor pressure depending on weather conditions, and is difficult to handle. In addition, a container with unprecedented pressure resistance is required for transport and storage.

Thus, in order to effectively use HFC-245fa as a substitute for HCFC_141b, there is a need for the development of technology to control its boiling point, solubility, etc.

The present invention provides a foaming agent, a premix, and a synthetic resin foam using the foaming agent which have solved or reduced the problems of HFC-245fa while maintaining the performance of HFC-245fa as a foaming agent. The main purpose is to provide a manufacturing method.

Disclosure of the invention

As a result of repeated studies in view of the above-mentioned problems in the prior art, the present inventor has found that a polyol and a polyisocyanate compound are reacted in the presence of a foaming agent to form a polyurethane, polyisocyanurate, or the like. It has been found that the above object can be achieved by using a specific foaming agent in the method for producing a synthetic resin foam of the present invention, and the present invention has been completed here.

That is, the present invention relates to the following method for producing a foam, a foaming agent, and a premix.

1. A method for producing a synthetic resin foam by reacting at least one polyol with at least one polyisocyanate compound in the presence of a foaming agent, wherein the foaming agent comprises at least one glycol. A method for producing a synthetic resin foam, which is a mixture containing a system compound and / or at least one amide compound and 1,1,1,3,3-pentafluoropropane. 2. The blowing agent is 1,1,1,3,3-pentafluoropropane and the total amount of at least one glycol compound and / or at least one amide compound is 1,1,1,3,3-pentafluoropropane. 2. The method according to the above 1, wherein the blowing agent contains 1,3,3_pentafluoropropane in an amount of 50% by weight or more.

3. (a) at least one glycol compound and / or at least one amide compound, (b) 1,1,1,3,3-pentafluoropropane and (c) at least one polyol Wherein the vapor pressure of the premix obtained is 95% or less with respect to the vapor pressure of the premix having the same composition except that (a) is excluded from the premix. The method described in.

4. The method according to the above item 1, wherein the blowing agent is a mixture containing at least one ethylene glycol compound and 1,1,1,3,3-pentafluoropropane.

5. The method according to item 4, wherein the ethylene glycol compound is at least one selected from the group consisting of compounds represented by the following formulas (Ι) to (ΙΠ):

C _a H _{2a + 1} (OCH ₂ CH ₂ ) _b OC _c H _2cn (I)

[Where a, b and c are independently a = 0, 1, 2, 3, 4, b = l, 2, 3, c = 0, 1, 2, 3, 4],

C _d H CO (OCH ₂ CH ₂ ) _e OCOC _f H _2W (II)

[Where d, e and f are independently d = 0, 1, 2, 3, 4, e = l, 2, 3, M), 1, 2, 3, 4] and

[Where i, j and k are independently i = 0, 1, 2, 3, 4, 2, 3, k = 0, 1, 2, 3, 4].

6. A blowing agent for producing a synthetic resin foam comprising at least one glycol compound and / or at least one amide compound and 1,1,1,1,3,3-pentafluoropropane.

7. 1,1,1 based on the total amount of at least one glycol-based conjugate and / or at least one amide-based compound and 1,1,1,1,3,3-pentaf / leo-propane 7. The foaming agent according to the above 6, which contains 1,3,3-pentafluoropropane in an amount of 50% by weight or more.

8. (a) at least one glycol compound and / or at least one amide compound, (b) l, l, l, 3,3-pentafluoropropane and (c) at least one polyol The foaming agent according to the above item 6, wherein the vapor pressure is 95% or less with respect to the vapor pressure of the premix having the same composition except that (a) is removed from the premix.

9. The blowing agent as described in 6 above, comprising an ethylene glycol compound and 1,1,1,3,3-pentafluoropropane. 10. The blowing agent according to the above 9, which is at least one member selected from the group consisting of ethylene glycol-based compound power s and compound power represented by the following formulas (Ι) to (ΠΙ):

C _a H ₂ a ₊ i (OCH ₂ CH ₂ ) _b OC _c H ₂₀ H (D

Five

(II)

Where d, e, and f are independently d = 0, 1, 2, 3, 4, e = l, 2, 3, ί ^ Ο, 1, 2, 3, 4, and

11. A premix comprising a blowing agent and at least one polyol, wherein the blowing agent comprises at least one glycol compound and / or at least one amide compound and 1,1,1,3. A premix which is a foaming agent containing 2,3-pentafluoropropane.

12. The blowing agent is selected from the group consisting of at least one glycol compound and / or at least one amide compound and 1,1,1,3,3-pentafluoropropane based on the total amount of 1,1,1,3,3-pentafluoropropane. 12. The premix as described in 11 above, which is a foaming agent containing 50% by weight or more of 1,3,3-pentafluoropropane.

15 13.Vapor pressure of the premix The premix power is 95% or less of the vapor pressure of the premix having the same composition except that at least one glycol compound and at least one amide compound are removed. 12. The premix according to 11 above.

14. The premix according to the above item 11, wherein the blowing agent is a blowing agent containing an ethylene glycol compound and 1,1,1,3,3-pentafluoropropane.

20 15. Ethylene glycol-based compound power The premix according to the above 14, which is at least one member selected from the group consisting of compounds represented by the following formulas (1) to (III):

C _a H _{2a + 1} (OCH ₂ CH ₂ ) _b OC _c H _{2c + 1} ①

Ο _ά Η _{2ά + 1} 00 (ΟΟΗ ₂ ΟΗ ₂ ) βΟΟ € _2Μ (II)

25 [where d, e and f are independently d = 0, 1, 2, 3, 4, e = l, 2, 3, M), 1, 2, 3, 4] and

[Where i, j and k are independently i = 0, 1, 2, 3, 4, j = l, 2, 3, k = 0, 1, 2, 3, 4] ₀

The present invention also includes a method for producing a foam, a foaming agent, and a premix as described below. 1A. In a method for producing a synthetic resin foam by reacting a polyol and a polyisocyanate compound in the presence of a foaming agent, the foaming agent comprises an ethylene glycol compound and 1,1,1,3,3- A method for producing a synthetic resin foam, which is a mixture containing pentafluoropropane.

2A. The blowing agent uses 1,1,1,3,3-pentafluoropropane based on the total amount of the ethylene glycol compound and 1,1,1,3,3-pentafluoropropane. The method according to 1A above, which is a foaming agent containing 50% by weight or more.

3A. A step of mixing (a) an ethylene glycol compound, (b) 1,1,1,3,3-pentafluoropropane and (c) a polyol, The method according to 1A or 2A above, wherein the vapor pressure of the mixture containing (c) is 90% or less with respect to the vapor pressure of the mixture of (b) and (c) having the same composition by weight as the mixture. That is, the vapor pressure of the obtained mixture containing (a;) to (c) is 90% or less of the vapor pressure of the mixture excluding the mixture power (a). Also, it may be 95% or less.

4A. The method according to any of 1A to 3A above, wherein the ethylene glycol compound is at least one selected from the group consisting of compounds represented by the following formulas (I) to (; ΠΙ):

C _a H _{2a + 1} (OCH ₂ CH ₂ ) _b OC _c H _{2c + 1} (D

[Where d, e and f are independently d = 0, 1, 2, 3, 4, e = l, 2, 3, ^ Ο, 1, 2, 3, 4] and

[Where i, j, and k are independently i = 0, 1, 2, 3, 4, j = l, 2, 3, k = 0, 1, 2, 3, 4].

5A. A foaming agent for producing a synthetic resin foam containing an ethylene glycol compound and 1,1,1,3,3-pentafluoropropane.

6A. Contains 1,1,1,3,3-pentafluoropropane in an amount of 50% by weight or more based on the total amount of the ethylene glycol compound and 1,1,1,3,3-pentafluoropropane The blowing agent according to 5A above.

7A, vapor pressure S when a premix containing (a) an ethylene glycol compound, (b) l, l, l, 3,3-pentafluoropropane and (c) polyol, The above 5A or 6A, wherein the same weight composition ratio is 90% or less with respect to the vapor pressure of the mixture of (b) l, l, l, 3,3-pentafluoropropane and (c) polyol. Foaming agent. That is, the obtained premiz containing (a) to (c) The vapor pressure of the tass may be 90% or less of the vapor pressure of the premix excluding the premix force (a). Also, it may be 95% or less.

8A. Ethylene glycol-based compound power The blowing agent according to any one of the above 5Α to 7Α, which is at least one selected from the group consisting of compounds represented by the following formulas (Ι) to (ΙΠ)

5 C _a H _{2a + 1} (OCH ₂ CH ₂ ) _b OC _c H _{2c + 1} (I)

C, H _{2d + 1} CO (OCH ₂ CH ₂ ) _e OCOC _j H _2M (II)

[Where d, e and f are independently d = 0, 1, 2, 3, 4, e = l, 2, 3, O, 1, 2, 3, 4] and

10 [where i, j, and k are independently i = 0, 1, 2, 3, 4, j = l, 2, 3, k = 0, 1, 2, 3, 4].

9A. A premix containing a foaming agent and a polyol, wherein the foaming agent is a foaming agent containing an ethylene glycol compound and 1,1,1,3,3-pentaf / leopropane.

10A. The blowing agent added 50% of 1,1,1,3,3-pentafluoropropane to the total amount of ethylene glycol compound and 1,1,1,3,3-pentafluoropropane. It is a foaming agent containing more than weight%

15 The premix described in 9A.

11A. The vapor pressure of the premix The above 9A or 9A, which is 90% or less of the vapor pressure of the mixture of the polyol and 1,1,1,3,3-pentafluoropropane having the same composition by weight as the premix. 1 Premix described in OA. That is, the vapor pressure of the premix is the same as the vapor pressure of the premix having the same composition except that the ethylene glycol compound is removed from the premix.

20 90% or less should be sufficient. Also, it may be 95% or less.

12A. The premix described in 9Α to 11 エチレン above, wherein the ethylene glycol compound is at least one selected from the group consisting of compounds represented by the following formulas (Ι) to (ΠΙ): : C _a H _{2a + 1} (OCH ₂ CH ₂ ) _b OC ₀ H _{2o + 1} (I)

[Where a, b, and c are independently a = 0, 1, 2, 3, 4, b = l, 2, 3, c = 0, 1, 2, 3, 4],

25 C _d H _{2d + 1} CO (OCH ₂ CH ₂ ) _e OCOC _f H _2M (II)

+ ₁ ΰΟ (0.Η ₂ α¾) ρ Η _{21ί + 1} (III)

[Where i, j and k are independently i = 0, 1, 2, 3, 4, j = l, 2, 3, k = 0, 1, 2, 3, 4]. The present invention relates to a blowing agent for producing a synthetic resin foam comprising at least one glycol compound and / or at least one amide compound and 1,1,1,1,3,3-pentafluoropropane. You. The blowing agent of the present invention contains one or more compounds selected from the group consisting of glycol compounds and amide compounds.

The present invention also includes a method for producing a synthetic resin foamed resin using the foaming agent. That is, the production method of the present invention is a method for producing a synthetic resin foam by reacting at least one kind of polyol and at least one kind of polyisocyanate compound in the presence of a foaming agent. The foaming agent is characterized in that it is a mixture comprising a glycol compound and / or an amide compound and 1,1,1,3,3-pentafluorolob bread.

Hereinafter, a mixture of at least one glycol compound such as an ethylene glycol compound and / or at least one amide compound and HFC-245fa may be referred to as a “mixed blowing agent”. A mixture containing a blowing agent and at least one polyol is sometimes referred to as a “premix”. The premix may contain a foaming catalyst, a stabilizer, a foam stabilizer, a flame retardant, and the like, in addition to the foaming agent and the polyol.

The boiling point of the blowing agent of the present invention at 1 atm is usually about 15 ° C. or higher, preferably about 17 to 35 ° C., and more preferably about 18 to 30 ° C.

* Glycol compound

Examples of the glycol compound used in the present invention include alkylene glycols such as ethylene glycol compounds, propylene glycol compounds, and butylene glycol compounds. The alkylene glycol usually has an alkylene group having about 2 to 4 carbon atoms, and preferably has an alkylene group having about 2 to 3 carbon atoms.

Examples of the ethylene glycol compound include, for example, compounds represented by the following formulas (Ι) to (ど).

C _a H _{2a + 1} (OCH ₂ CH ₂ ) _b OC ₀ H _{2c + 1} (I)

(II)

[Where d, e and f are independently d = 0, 1, 2, 3, 4, e = l, 2, 3, f ^ 0, 1, 2, 3, 4],

[Where i, j and k are independently i = 0, 1, 2, 3, 4, j = l, 2, 3, k = 0, 1, 2, 3, 4] In the formula (I), preferably, a and c cannot be 0 at the same time.

In the formula (III), k is preferably 1, 2, 3, 4 and more preferably 1, 2, 3.

Specific examples of the ethylene glycol-based compound represented by the formula (I) include, for example, ethylene glycol monoethylene, ethylene glycolone monomethinoleatene, ethylene glycolone resin methineoleatene, ethylene glycoloneleinee / leatenole, Ethylene glycolone retinole ethere, ethylene glycol monopropyl ethereole, ethylene glycolone dipropyle ether, ethylene glycol monolebutinoleate ethereole, ethylene glycolone resinebutinoleatee ethere, diethylene glycoloneole monomethyl ether, diethylene glycol dimethyl ether, Diethylene glycol monoethyl enolate, diethylene glycol olenoethyl enolate, diethylene glycol olenopropynoleate enole, diethylene glycol Dipropyl ether, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, triethylene glycol monomethyl ether ether, triethylene glycol dimethyl ether, triethylene glycol monoethyl ether, triethylene glycol / regeti / ether, triethylene glycol Examples thereof include ethylene glycol monopropynole ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, and triethylene glycol dibutyl ether. Further, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, etc. may be mentioned.

Specific examples of the ethylene glycol compound represented by the formula (II) include, for example, ethylene glycol monoformate, ethylene glycol diformate, diethylene glycol monophonate, diethylene glycol diformate, triethylene glycol monoformate. , Triethylene glycol diphonoremate, ethylene glycolone monoacetate, ethylene glycol diacetate, diethylene glycol monoacetate, diethylene glycolone resin acetate, triethylene glycol monoacetate, triethylene glycolone resin acetate, ethylene glycol monoethylene monoproate Pionate, ethylene glycolone resin propionate, diethylene glycolone propionate, diethylene glycol dipropione , Tri ethylene glycol monomethyl propylene Oneto, and triethylene glycol dipropionate may be exemplified.

Specific examples of the ethylene glycol-based compound represented by the formula (III) include, for example, ethylene glycol monomethyl enolate enole fonorate, ethylene glycol olenote enolate enole fonorate, and ethylene glycol propyl ether phonoreme. Mate, ethylene glycol methyl ether acetate , Ethylene glycol ethyl ether acetate, ethylene glycol propyl ether acetate, ethylene glycol methionoleate olenopropionate, ethylene glycol ethyl / leate olenopropionate, ethylene glycol oleoleate oleate / reb mouth pionate, gel Tylene glycol methyl ether acetate, diethylene glycol methyl ether phonolate, diethylene glycol ethyl ether formate, diethylene glycol propyl ether formate, diethylene glycol ethyl ether acetate, diethylene glycol propyl ether acetate, diethylene glycol methyl ether propionate, diethylene glycol Noleti / reether propionate, diethylene glycol Propylate Tenorepropionate, Triethylene glycol olenomethyl ether ether formate, Triethylene glycol etholenoyl ether phonoremate, Triethylene glycol propionoleate enole phonolemate, Triethylene glycol olenomethyl ether acetate, Triethylene glycol Examples thereof include ethylene glycol ethyl ether acetate, triethylene glycol propyl ether acetate, triethylene glycol methyl ether propionate, triethylene glycol ethyl ether propionate, and triethylene glycol propyl ether propionate. Furthermore, ethylene glycol butyl ether acetate, diethylene glycol butyl ether acetate and the like can be exemplified.

Further, a compound wherein b = 4 in the formula (I), a compound wherein e = 4 in the formula (II), and a compound wherein j = 4 in the formula (III) can be exemplified as the ethylene glycol-based compound. . Specific examples include tetraethylene dalicol, tetraethylene glycol dimethyl ether and the like.

Examples of the ethylene glycol-based compound include a polyester compound in which a and c are 1 or more in formula (I), a diester compound in which d and f are 1 or more in formula (II), and k and k in formula (III). Ethylene glycol 1 / resiacetate, ethylene glycolone rejectinoleatenole, ethyleneglycolonelemethinoleate 1 teracetate, diethylene glycol ethylethelenoacetate, which are preferred by ether esterolate conjugates having i of 1 or more Ethylene glycol monoethyl ether, of which diethylene glycol dimethyl ether or the like is more preferable, can also be suitably used. Examples of the ethylene glycol-based compound that can be suitably used include ethylene glycol dimethyl ether, ethylene glycol mono n-butyl ether acetate, ethylene glycol ethyl ether enorea acetate, and diethylene glycol butyl ether. Noreacetate, diethylene glycol getyl ether, diethylene glycol dibutinole ether, diethylene glycol resin, n-butyl ether, triethylene glycol resin, methyl ether, tetraethylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol mono, n -Butynoleatenol, ethylene glycolone monoisopropynolene, ethylene glycolonelen-propynoleatene, ethyleneglycolone _n- hexynoleatel, diethyleneglycolmonoethylatenole, diethyleneglycolmonomethyleatenole, Diethylene glycol monoisopropyl ether, diethylene glycol mono n-propyl / ether, diethylene glycol t-puchino Etenore, diethylene glycol n- to Kishinore Etenore, Jefferies Chile ring Ricoh Honoré mono n - can be illustrated Petit Honoré ether Honoré, triethylene glycol Honoré monomethyl E Ji ether, triethylene glycol monomethyl ether and the like. Also, for example, a propylene glycol-based compound such as tripropylene glycol monoethyl ether can also provide a desired effect. Examples of the propylene glycol compound include propylene glycol, dipropylene glycol, tripropylene glycol, propylene glycol monomethyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, and 3-methoxy-3-methylbutanol. , Dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethinole ether, tripropylene glycol monobutyl ether ether, 2-methoxy-1-propanol, tripropylene Glycol dimethyl ether, propylene glycol monomethinoleate enorea acetate, 3-methoxy-3-methylbutyl acetate, 3-methoxy It compounds such as chill acetate. Particularly, tripropylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-3-methylbutyl acetate, and 3-methoxybutyl acetate are preferred.

Examples of the glycol compound include a butylene glycol compound such as butylene glycol diacetate.

* Amide compounds

Examples of the amide compound used in the present invention include compounds represented by the following formulas (A) and (B).

Equation (A) R ^ ONR'R ³ [Wherein, R ¹ represents a hydrogen atom, a lower alkyl group or a phenyl group, and R ² and R ³ are the same or different and represent a hydrogen atom or a lower alkyl group. R ¹ and may form a heterocycle with the carbonyl carbon atom to which R ¹ is bonded and the nitrogen atom to which R ² is bonded. ]

Formula) R ⁴ R ⁵ NCONR ⁶ R ⁷

[Wherein, R ⁴ , R \ R ⁶ and R ⁷ are the same or different and each represent a hydrogen atom or a lower alkyl group. R ⁴ and R ⁶ may form a heterocyclic ring with the nitrogen atom to which R ⁶ is bonded, the nitrogen atom to which R ⁴ is bonded, and a carbonyl carbon. ]

In formula (A), the number of carbon atoms of the lower alkyl group represented by R ² or R ³ is usually about! To 2, and a methyl group is preferable.

R ¹ is a hydrogen atom, a lower alkyl group or a phenyl group, preferably a hydrogen atom or a methyl group.

R ² is a hydrogen atom or a lower alkyl group, preferably a lower alkyl group, particularly preferably a methyl group.

R ³ is a hydrogen atom or a lower alkyl group, preferably a lower alkyl group, and particularly preferably a methyl group.

Further, in the formula (A), R ¹ and R ² may form a heterocycle with the carbonyl carbon atom to which R ¹ is bonded and the nitrogen atom to which R ² is bonded. That is, the compound of the formula (A) may be a cyclic amide compound. Examples of the heterocycle include a 5-membered ring.

The amide compounds represented by the formula (A) include Ν, Ν-dimethylformamide, Ν, Ν-dimethylacetamide, Ν, Ν-dimethylpropionamide, Ν-methylformamide, Ν-methylacetamide, Ν -Methylpropionamide, Ν-methylbenzamide and the like. Examples of the cyclic amide compound represented by the formula (Α) include Ν-methylpyrrolidone and the like. As the amide compound represented by the formula (Α), a compound in which both R ² and R ³ are a lower alkyl group is preferable, and Ν, Ν-dimethylformamide, Ν, Ν-dimethylacetamide, Ν, Ν-dimethylpropionamide, Ν-methylpyrrolidone and the like are preferred.

In the formula (Β), the lower alkyl group represented by R ⁴ , R ⁵ , R ⁶ or R ⁷ usually has about 1 to 2 carbon atoms, and is preferably a methyl group. Further, R ⁴ and R ⁶ may form a heterocycle with the nitrogen atom to which R ⁶ is bonded, the nitrogen atom to which R ⁴ is bonded, and a carbonyl carbon. That is, the compound of the formula (B) may be a cyclic compound. Examples of the heterocycle include a 5-membered ring.

Examples of the amide compound represented by the formula (B) include, for example, tetramethylurea. Examples of the cyclic compound represented by the formula (B) include 1,3-dimethylimidazolidinone.

As the ethylene glycol compound, a compound having high compatibility with HFC_245fa and / or polyol is preferable. For example, after shaking HFC-245fa, ethylene glycol-based compound, and polyol for about 10 minutes, ethylene glycol-based compounds that do not phase separate even after being left at about 0 to 25 ° C for about 5 hours are preferable. ,. Similarly, a glycol-based compound or an amide-based compound other than an ethylene glycol-based compound is preferably a compound having the above-mentioned properties, which is preferably a compound having high compatibility with HFC-245fa and / or polyol. From the viewpoint of compatibility with HFC-245fa and / or polyol, the compounds having the specific names described above can be preferably used. The higher the compatibility of glycol compounds and / or amide compounds such as ethylene glycol compounds and / or amide compounds with HFC-245fa and / or polyol, the more the mixture of polyol and blowing agent is placed in an open system and foaming when placed in an open system The loss (dispersion amount) of the agent can be reduced. Also, the vapor pressure of the mixture can be reduced.

As the ethylene glycol compound, a flame retardant compound is preferable. However, it is not necessary for the ethylene glycol compound to be completely nonflammable, as long as it can maintain flame retardancy when used in a mixture with non-flammable HFC-245fa. As the ethylene glycol-based compound, it is preferable to use a dangerous substance of the fourth class, which has a flame resistance of about 3 stones or more. The flame retardancy of the ethylene glycol compound is not particularly limited as long as it has the above-described flame retardancy. Similarly, daricol compounds and amide compounds other than ethylene glycol compounds are preferably flame-retardant, but it is not necessary for the glycol compounds and Z or amide compounds to be completely nonflammable. When a mixture of the above is used, it is only necessary that the mixture can maintain flame retardancy. Further, glycol-based compounds and / or amide-based compounds having the above-mentioned properties are preferred. The use of a flame-retardant dalicol-based compound and / or amide-based compound makes it possible to keep the blowing agent flame-retardant and to maintain the flame retardancy required during on-site foaming. `` Class 4 hazardous materials, flame retardancy of 3 stones '' is the flash point Is a liquid having a flammability of 70 ° C or more and less than 200 ° C. Whether it is liquid or not is determined at 1 atmosphere and 20 ° C. “Hazardous material class 4, flame retardant with 3 stones or more” means that the flash point is a flammable liquid with a flash point of 70 ° C or more. For example, the flash point of diethylene glycol monoethyl ether acetate is 110 ° C, and the flash point of ethylene glycol diacetate is 96 ° C, both of which are liquid at 20 ° C. Therefore, they are classified as dangerous goods class 4 and 3 stones.

The mixing ratio between HFC-245fa and the glycol-based compound or amide-based compound can be arbitrarily selected according to the application, the composition of the synthetic resin foam raw material, and the like. For example, at about 30 ° C, (a) at least one glycol compound and / or at least one amide compound

The mixture (premix) containing (b) HFC_245fa and (c) at least one polyol has the same vapor pressure as that of the mixture having the same composition except that (a) is excluded from the mixture. It is preferable to set the ratio of HFC-245fa to the glycol compound and the Z or amide compound so as to be about 95% or less, preferably about 90% or less, and more preferably about 80% or less. That is, (a) at least one glycol compound and / or at least one amide compound

15 Compound, (b) HFC-245fa and (c) a mixture (premix) comprising at least one polyol having a vapor pressure of the same weight composition ratio as that of the above mixture (b) and (c) a vapor of the mixture having a strong force. It is preferable to set the ratio of HFC-245fa to the glycol compound and / or the amide compound so that the pressure is about 95% or less, preferably about 90% or less, more preferably about 80% or less.

20 More specifically, (a) at least one ethylene glycol compound: A parts by weight, (b) HFC-245fa: B parts by weight (c) at least one polyol: C parts by weight Taking the case of a foaming agent as an example, the vapor pressure of the foaming agent (a) to (c) is (b) the weight composition ratio of (c) at least one polyol to HFC-245fa is B : HFC- so that the vapor pressure of the mixture of (b) and (C) is about 95% or less, preferably about 90% or less, and more preferably about 80% or less.

It is preferable to set the ratio between 25 245fa and at least one ethylene glycol compound. The mixture of HFC-245fa and at least one ethylene glycol compound having a total capacity of about 20 to 70 parts by weight with respect to 100 parts by weight of at least one polyol is used for measuring the vapor pressure ratio. . Similarly, when using a glycol compound and / or an amide compound other than the ethylene glycol compound, the mixing ratio of HFC-245fa to at least one glycol compound and / or at least one amide compound is It can be arbitrarily selected according to the application, the composition of the synthetic resin foam raw material, and the like. Further, the same mixing ratio as in the case of the ethylene glycol compound can be employed.

Alternatively, the boiling point of the premix (the temperature at which the vapor pressure of the premix becomes 1 atm) is usually about 15 ° C or more, preferably about 17 to 35 ° C, and more preferably about 18 to 30 ° C. Preferably, the ratio of HFC-245fa to at least one ethylene glycol compound is set so that the mixture is mixed with at least one polyol. When a glycol compound and / or an amide compound other than an ethylene dalicol compound is used, it is preferable to mix the polyol with the polyol so that the same ratio as in the case of the ethylene dalicol compound is used.

The compounding amount of HFC_245fa in the blowing agent of the present invention is usually about 50% by weight or more, preferably about 65 to 99% by weight, based on the total amount of HFC-245fa and at least one ethylene glycol compound. It is preferably about 75 to 98% by weight. The same applies when using a glycol compound and / or an amide compound other than the ethylene glycol compound.

The blowing agent of the present invention may contain another blowing agent. That is, the mixed foaming agent may be used alone or in combination with another foaming agent. Examples of foaming agents that can be used in combination include, for example, HFC134a (l, l, l, 2-tetrafluoroethane) and HFC227ea (l, l, l, 2, 3, 3, 3-heptafluoropropane). Low boiling halogen hydrocarbons; examples include air, nitrogen, and inert gases such as carbon dioxide. Such a foaming agent has a low boiling point of not more than o ° c, and is usually stored in a premix state, which is often added and used at the time of foaming in the production of a foam. For example, as the low boiling halogenated hydrocarbon, a low boiling halogenated hydrocarbon having a boiling point of about −30 to 0 ° C. at 1 atm (about 0.1 MPa) can be exemplified. When another blowing agent is used, the proportion of the total amount of at least one ethylene glycol compound and HFC-245fa in all the blowing agents is preferably about 20% by weight or more, particularly preferably about 40% by weight or more. Similar ratios can be used for dalicol-based compounds and / or amide-based compounds other than ethylene glycol-based compounds. The blowing agent of the present invention may contain water. That is, the mixed foaming agent may be used alone or in combination with water. In many cases, the mixed blowing agent is used in combination with water. This is because carbon dioxide gas is generated at the time of foaming by caloring water, and the carbon dioxide gas contributes to foaming. However, if too much water is added, the heat insulation performance of the foam may be reduced. The amount of water added is usually about 60 mol% or less based on the total amount of HFC-245fa and water. By setting it within this range, a highly heat-insulating foam can be produced more reliably.

Further, the foaming agent of the present invention may optionally contain a decomposition inhibitor. Examples of the decomposition inhibitor include nitro compounds such as nitrobenzene and nitromethane;-aromatic hydrocarbons such as methynolestyrene and monoisopropenyltoluene; aliphatic unsaturated hydrocarbons such as isoprene and 2,3-dimethylbutadiene; Epoxy compounds such as 2-butylene oxide and epichlorohydrin; phenol compounds such as pt-butyl catechol and 2,6-di-t-butyl-ρ_tarezole; chloroacetate compounds such as isopropyl chloroacetate It can be shown as a preferred one.

The mixing ratio of the decomposition inhibitor can be appropriately set according to the type of the inhibitor, and is usually about 0.05 to 5 parts by weight based on 100 parts by weight of the blowing agent of the present invention. The decomposition inhibitor may be mixed with a foaming agent in advance, or may be separately added at the time of foaming.

The amount of the foaming agent of the present invention can be appropriately set according to the composition and the like.HFC-245fa power is usually about 1 to 60 parts by weight, preferably 100 parts by weight of at least one kind of polyol. Is contained in an amount of about 10 to 50 parts by weight, more preferably about 20 to 45 parts by weight.

In the production method of the present invention, a synthetic resin foam is produced by reacting at least one kind of polyol and at least one kind of polyisocyanate conjugate in the presence of a foaming agent. Examples of the obtained synthetic resin foam include a polyurethane foam and a polyisocyanurate foam.

Raw materials other than foaming agents such as polyols and polyisocyanate compounds are not particularly limited, and known materials can be used. The following can be exemplified as these.

Examples of the polyisocyanate compound include organic isocyanates such as aliphatic, alicyclic, and aromatic organic isocyanates described in Keiji Iwata, Polyurethane Resin Handbook, pp. 71-98, Nikkan Kogyo Shimbun. Can be used. The most commonly used poly Examples of the socyanate include 2,4-tolylene diisocyanate (2,4-TDI) and 2,6-tolylene diisocyanate (2,6-TDI). Among them, 2,4-TDI / 2,6 — A mixture in which the weight ratio of TDI is about 80Z20 or about 65/35 is particularly commonly used, and can be suitably used in the present invention. In addition, polyphenylpolymethylene polyisocyanate (crude mono-MDI) obtained by subjecting a condensate of aniline and formaldehyde to phosgene treatment is also commonly used and can be suitably used in the present invention.

As the polyol, for example, polyether polyols, polyester polyols, and the like described in “Keiji Iwata, Polyurethane Resin Handbook, pp. 99-117, Nikkan Kogyo Shimbun” can be used.

The polyether polyol can be obtained, for example, by reacting an initiator having an active hydrogen atom with an alkylene oxide. For example, using ethylene glycol, trimethylolpropane, glycerin, triethanolamine, ethylenediamine, methyl dalcodite, tolylenediamine, sorbitol, sucrose, etc. as initiators, and using ethylene oxide, propylene oxide, etc. as alkylene oxides, It is possible to use a polyether polyol having a functional group number of about 2 to 8 and a hydroxyl value of about 300 to 800 mg KOH / g obtained by reacting both.

Examples of the polyester polyols include condensed polyester polyols obtained by dehydration condensation of adipic acid and dalicol or toluene; rataton-based polyesters and polycarbonate diols obtained by ring-opening polymerization of force prolatatam. Polyester polyols having a group number of about 2 to 4 and a hydroxyl value of about 250 to 500 mgKOH / g can be suitably used.

The mixing ratio of the polyol and the polyisocyanate compound can be determined as appropriate, but the active hydrogen in the polyol relative to 1 equivalent of the isocyanate group in the polyisocyanate compound is usually 1 to 3 equivalents. It is about.

In the production method of the present invention, a polyol and a polyisocyanate compound are foamed in the presence of a foaming agent and a catalyst to produce a synthetic resin foam. As such a catalyst, a known catalyst such as a tertiary amine, an organometallic compound, or a mixture thereof can be used. The amount of the catalyst to be used is generally about 0.01 to 10 parts by weight, preferably about 0.1 to 5 parts by weight, based on 100 parts by weight of the polyol. Examples of tertiary amines that can be used as catalysts include monoamines such as triethylamine and dimethylcyclohexanolamine; tetramethinoleethylenediamine, tetramethylhexamethylenediamine, and N, N, N, N, -tetramethylamine. Diamines such as xan-1,6-diamine; cyclic amines such as triethylenediamine and 1,2-dimethylimidazole; and alcoholamines such as dimethylaminoethanol. Examples of the organometallic compound include star nasoctoate, dibutyltin dilaurate, dibutyltin diacetate, and the like. In the production method of the present invention, additives known in the art (for example, a foam stabilizer) may be used. Examples of the foam stabilizer include silicone surfactants and fluorine-containing surfactants, and more specifically, surfactants based on polysiloxane-polyalkylene block copolymer, methylpolysiloxane, and the like are used. can do. Examples of the fluorinated surfactant IJ include perfluoroalkylethylene oxide adducts, perfluoroalkyl sulfonates, perfluoroalkyl group-containing oligomers, and the like. The amount of the foam stabilizer is usually about 0.1 to 10 parts by weight based on 100 parts by weight of the polyol. Of course, the present invention includes embodiments in which no fluorine-containing surfactant is used.

The manufacturing conditions are good according to the usual method. For example, any device can be used as long as it can uniformly mix the raw materials.Specifically, using a mixer, a foaming machine, or the like, a polyol, a polyisocyanate compound, and a foaming agent are used. The desired foam can be obtained by thoroughly mixing and shaping each raw material such as a catalyst, a catalyst, and other additives. When the foaming agent and other additives are dissolved in the polyol component in advance and used as a premix, a force that makes it easy to obtain a uniform foam is not limited to this. It may be dissolved in advance. According to the present invention, a foaming agent having improved solubility in polyol can be obtained while maintaining the performance of HFC-245fa as a foaming agent. That is, according to the present invention, it is possible to obtain a synthetic resin foam having the same heat insulating property and mechanical strength as when HFC-245fa is used alone as a foaming agent.

The blowing agent of the present invention has no risk of breaking the ozone layer.

According to the present invention, a foaming agent having an appropriate boiling point can be obtained.

When the mixture of the blowing agent of the present invention and the polyol is placed in an open system, the loss of the blowing agent can be reduced as compared with the case of the mixture comprising HFC-245fa and the polyol. Since the mixture (premix) of the blowing agent and the polyol of the present invention has an appropriate vapor pressure, the handling is lower than that of the mixture of HFC-245fa and the polyol.

As the mixture (premix) of the blowing agent and the polyol of the present invention, a conventional container can be used as a container for transportation and storage, and it is not necessary to use a container having particularly high pressure resistance.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. The present invention is not limited to these Examples.

The polyol and the blowing agent used in the following examples are as follows. Polyol A: Polyester polyol with a hydroxyl value of 300 mgKOH / g

Polyol B: Polyether polyol with hydroxyl value of 440 mgKOH / g

Mixed blowing agent A: Mixture of ethylene glycol diacetate and HFC-245fa

Blending agent B: Mixture of diethylene glycol monoethyl ether and HFC-245fa Blending agent C: Mixture of diethylene glycol ethyl ether acetate and HFC-245fa

Mixed foaming agent D: Mixture of diethylene glycol dimethyl ether and HFC-245fa Mixed foaming agent E: Mixture of dipropylene glycol monomethyl ether and HFC-245fa Mixed foaming agent F: Mixture of N, N-dimethylacetamide and HFC_245fa

The proportion of HFC-245fa in the mixed foaming agents A to E was 85% by weight. The glycol-based compounds contained in the foaming agents A to E all have the flame retardancy of more than three types of dangerous goods, three stones. Since HFC-245fa is a non-dangerous substance, foaming agents A to E are judged to be flame retardant.

Example 1: Compatibility with polyol

In a glass bottle with a screw stopper with a capacity of 50 ml, put a total of 30 _g of each mixed foaming agent (10 _g) and each polyol (20 _g) , shake with a shaker for 10 minutes, and leave at room temperature for 5 hours to determine whether separation has occurred. Was visually confirmed. Also, the presence or absence of separation was confirmed in the same manner as described above, except that 10 g of HFC-245fa and 20 g of each polyol were used. Table 1 shows the results. The judgment was made based on the following criteria.

A; Uniformly dissolved, no separation. B: Not separated, but difficult to be uniform. C; separation The foaming agent of the present invention

Poly

All Foaming agent Foaming agent Foaming agent Foaming agent Foaming agent Foaming agent HFC-A B C D E F 245fa

A A A A A 'A A B

BAAAAAAA Results in Table 1 As can be clearly seen, the mixed foaming agents A to E show good compatibility with the polyol at the mixing ratio actually used and form a stable premix. Was confirmed.

Examples 2 to 5: Scattering from premix

The mixed blowing agents A, B, C or D and the polyol B were mixed at a weight ratio of 47: 100 (weight ratio of glycol compound: HFC-245fa: polyol = 7: 40: 100). The obtained mixture was placed in a Petri dish, left at 40 ° C. for 1 hour, and the amount of scattering was compared. As a comparison, when the weight ratio of HFC-245fa to polyol B was 40: 100, the amount of scattering was measured in the same manner, and the relative value was calculated by setting the amount of scattering at this time to 1. The results are shown in Table 2 below.

Table 2

By using the mixed foaming agent, the amount of scattering was significantly reduced. That is, the loss when the premix was placed in an open system could be greatly reduced.

Examples 6-9 and Comparative Example 2: Vapor pressure of premix

The mixed blowing agents A, B, C or D and the polyol B were mixed at a weight ratio of 47: 100, respectively, sealed in a metal container, air was excluded, and the vapor pressure was measured at 20 ° C and 30 ° C. The vapor pressure of the premix when the weight ratio of HFC-245fa to Polyol A was 40: 100 was measured in the same manner. The results are shown in Table 3 below. Table 3

By using the mixed blowing agent, the vapor pressure of the premix was able to be significantly reduced as compared with the case where HFC-245fa was used alone. In addition, the boiling point of the premix could be increased to 20 ° C or higher, as is clear from the fact that the vapor pressure at 20 ° C was lower than 0.1 MPa.

Examples 10 and 11

With respect to 100 parts by weight of polyol B, 1.5 parts by weight of silicone foam stabilizer, 1 part by weight of water, N, N, Ν ', N'-tetramethylhexane-1,6-diamine and the compounds described in Table 3 The blowing agent was mixed and stirred vigorously. The catalyst, Ν, Ν, Ν ', Ν'-tetramethylhexane-1,6-diamine, was prepared in the required amount to achieve a rise time of 70 seconds. This stirred mixture was mixed with 112 parts by weight of crude polymethylenepolyphenylisocyanate (manufactured by Nippon Polyurethane Industry, MR-100), and vigorously stirred to foam to obtain a rigid polyurethane foam. The amount of the foaming agent was adjusted so that the core density of the foam was 25 ± 1 kgZm ³ .

Table 4 shows the measurement results of the physical properties of the obtained foam one day after foaming and aging for one week at -20 ° C or room temperature (20 ° C). In addition, the evaluation method of the foam conformed to JIS A 9514.

Table 4

In addition, the amount of the blowing agent in the table is shown in parts by weight based on 100 parts by weight of the polyol. As is clear from the results in Table 4, it was confirmed that by using the blowing agent of the present invention, a polyurethane foam having excellent characteristics could be obtained. That is, when the foaming agent of the present invention was used, a foam having the same thermal conductivity and compressive strength as when HFC-245fa was used alone could be obtained. In addition, the rate of change in thermal conductivity and the rate of change in strength were similar to those obtained when HFC-245fa was used alone.

Examples 12 and 13

The amount of scattering from the premix was measured in the same manner as in Examples 2 to 5, except that the mixed blowing agent E or F was used. The results are shown in Table 2.

By using the mixed foaming agent E or F, the amount of flying was significantly reduced. That is, the loss when the premix was placed in an open system could be greatly reduced.

Example 14

The vapor pressure of the premix was measured in the same manner as in Examples 6 to 9, except that the mixed blowing agent E was used. Table 3 shows the results.

By using the mixed foaming agent E, the vapor pressure of the premix could be significantly reduced compared to the case where HFC-245fa was used alone. In addition, the boiling point of the premix could be increased to 20 ° C or higher, as is apparent from the fact that the vapor pressure at 20 ° C was lower than 0.1 MPa.

Claims

The scope of the claims

1.A method for producing a synthetic resin foam by reacting at least one kind of polyol and at least one kind of polyisocyanate compound in the presence of a foaming agent.

Production of a synthetic resin foam characterized by being a mixture containing one glycol compound and / or at least one amide compound and 1,1,1,3,3-pentafluoropropane Method.

2. The blowing agent is at least 1,1 based on the total amount of at least one glycol compound and / or at least one amide compound and 1,1,1,3,3-pentafluoropropane. The method according to claim 1, which is a blowing agent containing at least 50% by weight of 1,1,3,3-pentafluoropropane.

3. (a) at least one glycol compound and / or at least one amide compound, (b) 1,1,1,3,3-pentafluoropropane and (c) at least one compound A step of preparing a premix containing the polyol of the present invention, wherein the vapor pressure of the obtained premix is the same as that of the premix having the same composition except that (a) is removed from the premix. 2. The method according to claim 1, which is 95% or less.

4. The method according to claim 1, wherein the blowing agent is a mixture containing at least one ethylene glycol compound and 1,1,1,3,3-pentafluoropropane.

5. The method according to claim 4, wherein the ethylene glycol compound is at least one selected from the group consisting of compounds represented by the following formulas (1) to (III):

C _a H _{2a + 1} (OCH ₂ CH ₂ ) _b OC _c H _{2o + 1} (I)

_CdH . _{_{0 (0.Η 2 α¾) β Ο}} . ΟΟΗ _2Μ (II)

Where d, e and f are independently d = 0, 1, 2, 3, 4, e = l, 2, 3, 0, 1, 2, 3, 4] and. _{+1 for} 0 (0. 0 ₊₁ (III)

7. 1,1,1,3 based on the total amount of at least one glycol compound and / or at least one amide compound and 1,1,1,3,3-pentafluoropropane 7. The blowing agent according to claim 6, comprising at least 50% by weight of 1,3-pentafluoropropane.

8. (a) at least one glycol compound and / or at least one amide compound, (b) l, l, l, 3,3-pentafluoropropane and (c) at least one The foaming according to claim 6, wherein the vapor pressure of the premix containing the polyol is 95% or less with respect to the vapor pressure of the premix having the same composition except that (a) is removed from the premix. Agent.

9. The blowing agent according to claim 6, comprising an ethylene glycol compound and 1,1,1,3,3-pentafluoropropane.

10. Ethylene glycol-based compound power A compound power represented by the following formulas (1) to (III): A group power selected from at least one selected from the group consisting of:

C _a H _{2a + 1} (OCH ₂ CH ₂ ) _b OC _c H _{2c + 1} (I)

[Where d, e and f are independently d = 0, 1, 2, 3, 4, e = l, 2, 3, 0, 1, 2, 3, 4] and

[Where i, j and k are independently i = 0, 1, 2, 3, 4, j = l, 2, 3, k = 0, 1, 2, 3, 4].

11. A premix comprising a blowing agent and at least one polyol, wherein the blowing agent comprises at least one glycol compound and / or at least one amide compound and 1,1,1,3,3. -Premix which is a foaming agent containing pentafluoropropane.

12. The foaming agent is 1,1,1,3,3-pentafluoropropane with respect to the total amount of at least one glycol compound and / or at least one amide compound and 1,1,1,3,3-pentafluoropropane. 12. The premix according to claim 11, which is a foaming agent containing 1,3,3_pentafluoropropane in an amount of 50% by weight or more.

13.The vapor pressure of the premix is 95% or less of the vapor pressure of the premix of the same composition except that the premix power and the at least one glycol compound and at least one amide compound are excluded. The premix according to claim 11, which is:

14. The premix according to claim 11, wherein the blowing agent is a blowing agent containing an ethylene glycol compound and 1,1,1,3,3-pentafluoropropane.

15. The premix according to claim 14, wherein the ethylene glycol compound is at least one selected from the group consisting of compounds represented by the following formulas (i) to (m):

C _a H _{2a + 1} (OCH ₂ CH ₂ ) _b OC ₀ H _{2c + 1} (I)

Where d, e and f are independently d = 0, 1, 2, 3, 4, e = l, 2, 3,), 1, 2, 3, 4] and